Phthalocyanine colouring matters



3,4Z,fi%3 Fatentecl July 3, 1952 3,042,683 PHTHALOCYANINE COLOURING MATTERS Harold Thompson Howard and Christopher David Marrable, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed June 17, 1960, Ser. No. 36,739 Claims priority, application Great Britain July 2, 1959 Claims. (Cl. 260-3145) This invention relates to phthalocyanine colouring matters.

It is known to colour cellulose acetate rayon by a mass colouration process in which a suitable colouring matter is incorporated with a solution of cellulose acetate in acetone and the mixture is then spun into filaments.

The present invention relates to new colouring matters of the phthalocyanine series which are soluble in acetone and are suitable for use in the mass colouration of cellulose acetate rayon.

According to the invention we provide new colouring matters of the formula wherein Pc stands for the residue of a stable metal phthalocyanine colouring matter, -X stands for CH or 40 R stands for a lower alkylene radical, R stands for a lower alkyl or an aryl radical, R stands for hydrogen or a lower alkyl radical or for the group R .O.CO.R where R, is a lower alkylene radical,-

and n is any number from 2 to 8.

As examples of stable metal phthalocyanine colouring matters there may be mentioned the phthalocyanines of copper, cobalt, nickel, iron, aluminum and chromium, and their derivatives in which the phthalocyanine nucleus is substituted, for example by halogen atoms such as chlorine, or aryl radicals such as phenyl and tolyl which may be attached directly to the phthalocyanine nucleus or through a linking atom or group for example a S, --CO- or SO NH- group. The radical X- in the above formula may be attached directly to the phthalocyanine nucleus or to a pendant aryl radical which itself is attached directly or through a linking atom or group to the phthalocyanine nucleus.

Those new colouring matters of the invention in which X stands for SO; may also contain not more than one sulphonic acid group, either attached directly to the ,phthalocyam'ne nucleus or to a pendant aryl radical.

As examples of lower alkylene radicals which may be represented by R and R there may be mentioned ethylene, 2-ethy1ethylene and Z-n-propylethylene. As examples of lower alkyl or aryl radicals which may be represented by R there may be mentioned methyl, ethyl,-

phenyl and chlorophenyl and as examples of lower alkyl radicals which may be represented by R there may be mentioned methyl and ethyl As specific examples of the colouring matters of our invention there may be mentioned copper di, triand tetra-[di-(B acetoxyethyl) aminomethyHphthalocyanine, copper triand tetra-[di-(fi-acetoxyethyl)arninomethyl] tetra-(tolylmercapto)phthalocyanine, copper di, tri-, and

tetra-[di (B propionyloxyethyl)aminomethyHphthalocyanine, copper di, triand tetra-[di-(B-benzoyloxyethyl) aminomethyflphthalocyanine, copper tetra-[di (5 acetoxyethyl aminomethyl] tetraphenylphthalocyanine copper octa [di (B acetoxyethyl)aminomethyl1octaphenylphthalocyanine, copper triand tetra-(fl-acetoxyethylsulphamyl)phthalocyanine, copper triand tetra-[di-(B-acetoxyethyl) sulphamyflphthalocyanine, copper tetra [N- ethyl-N (,8 7 acetoxyethyl)sulphamyjphthalocyanine and copper tri-[N-(fi-acetoxyethyl) N (B acetoxypentyl) sulphamyHphthalocyanine, nickel and cobalt tri-(B-acetoxyethylsulphamyl)phthalocyanine and copper tetra-4- chloro-tri- B-acetoxyethyl) sulphamylphthalo cyanine.

According to a further feature of the invention we provide a process for the manufacture of the new colouring matters as hereinbefore defined which comprises treating a hydroxy compound of the formula with the anhydride or chloride of a carboxylic acid of the formula R COOH wherein Pc, X, and R have the meanings previously stated, and R stands for hydrogen or a lower alkyl radical or for the group -R OH wherein R is a lower alkylene radical.

The process of the reaction may conveniently be carried out by heating, for example to the boiling point, a suspension of the hydroxy compound in the acid anhydride until a solution is obtained. This usually requires between 1 and 4 hours. To isolate the product the solution may, for example, be diluted with about 10 times its volume of cold water and the mixture neutralised by addition of a dilute alkali such as sodium carbonate. The solid so precipitated may then be isolated by filtering, washing and drying. If desired the product may be purified by dissolving it in acetone, filtering from insoluble matter and evaporating the acetone solution to dryness.

Hydroxy compounds suitable for use in the process of the invention may be obtained by reaction of a chloro compound of the formula PcX-Ol wherein Po and X have the meanings already stated with the appropriate hydroxyamino compound. Thus the hydroxy compounds in which -X stands for CH may be obtained from chloromethyl phthalocyanines and the hydroxy compounds in which X stands for SO may be obtained from phthalocyanine sulphonyl chlorides. Reaction of a chloro compound of the above formula wherein X stands for SO with a hydroxyamino compound may result in the formation of a product which contains sulphonic acid groups in addition to substituted sulphonamide groups. Such products are nevertheless suitable for use in the process of the invention, provided that they do not contain more than one sulphonic acid group.

According to a further feature of the invention we provide an alternative process for the manufacture of the new colouring matters as hereinbefore defined which comprises treating a halogeno compound of the formula Pcl-X-halthe alternative process of the invention there may be mentioned 13-acetoxyethylamine and di(fi-acetoxyethyl)amine.

The new colouring matters of the invention are suitable for use in the colouration of. plastics and lacquers,

and being readily and completely soluble in acetone they are especially suitable for use in the mass colouration of cellulose acetate rayon, giving blue to green shades of high fastness to light and to wet treatments.

The new colouring matters in which Pc stands for cop- V per phthalocyanine form a preferred feature of the in- 7 Example 1 5 parts of a mixture of copper diand tri-[di-(B-hydroxyethyD-aminomethyl]phthalocyanine is stirred with 25 parts of acetic anhydride and boiled under reflux for 1 hour. The mixture is cooled and diluted with 200 parts of cold water, made just alkaline to Brilliant Yellow paper by the addition of aqueous sodium carbonate solution. *The product is filtered oil and dried.

The dry solid is dissolved in acetone and the solution filtered from insoluble material. By evaporation of the acetone a mixture of copper diand tri-[di-(fi-acetoxyethyl)aminomethyflphthalocyanine is obtained. The product is suitable for use in the mass colouration of cellulos'e acetate rayon and gives bright greenish blue shades of high fastness to light and wet treatments. 7

The mixture of copper diand 11i-[di(,8-hydroxyethyl)- aminomethyflphthalocyanine used in this example may be obtained as described in Example 5 of British application No. 11,399/58.

l- Example 2 5 parts of a mixture of copper triand tetra-[di-(fl-hydroxyethyl) aminomethyl] tetra-(tolylmercapto)phthalocyanine is stirred with 25 parts of acetic anhydride and boiled under reflux for 1 hour. The mixture is cooled and diluted with 200 parts of Water, made just alkaline to Brilliant Yellow paper with 10% aqueous sodium carbonate solution. The product is filtered off, washed with waterand dried. The mixture of copper triand tetra- [di (,B -acetoxyethyl)aminomethyl] tetra (tolylmercapto) phthalocyanine so obtained is completely soluble in acetone and is suitable for use in the mass colouration of cellulose acetate rayon giving bright green shades of high fastness to light and wet treatments.

p The mixture of copper triand tetra[di-(,8-hydroxyethyl) -aminomethyl] tetra (tolylmercapto)phthalocya nine used in this example may be obtained as described in Example 9 of British application No. l'1,399/58.

-- V Example 3 In place of the 25 parts of acetic anhydride used in Example 2 there'is used 25 parts of propionic anhydride. The mixture of copper triand tetra-[di-(,S-propionyloxyethyl)aminomethyl] tetra (tolylmercapto)phthalocyanine so obtained is completely soluble in acetone and is suitable for use in the mass colouration of cellulose acetone rayon, giving fast green shades.

V Example 4 In place of the 25 parts of acetic 'anhydride used in Ex ample 2,there is used 25 parts of benzoic anhydride and 'themixture is stirred at 140 C. for 1 hour. The mix ture of copper triand tetra-[di(fi-benzyloxyethyl) amino methyl] tetra (tolylmercapto)phthalocyanine so obtained is's'oluble in acetone and may be used in the mass colouration of cellulose acetate rayon, giving fast green shades.

' Example 5 V In place of the of: the mixture of copper-tri and tetra [di (6 hydroxyethyDaminornethyl]tetra (tolylmercapto) phthalocyanine used in Example 2 there is [diQB acetoxyethyl) aminomethyl]tetraphenylphthalocyanine so obtained is soluble in acetone and gives fast green shades when used in the mass colouration of cellulose acetate rayon.

Copper tetra [di (18 hydroxyethyl) aminomethyntetra phenylphthalocyanine may be obtained by reacting copper tetra (chloromethyl)tetraphenylphthalocyanine obt-ained as described in Example 13 of British patent specification No. 586,340) with di-(flt-hydroxyethyhamine.

Example 6 In place of the 5 parts of the mixture of copper triand tetra [di (p hydroxyethyl)aminomethyl]tetra(tolylmercapto)-phthalocyanine used in Example 2, there is used 5 parts of copper octa-[di(p-hydroxyethyl)aminomethyl]octaphenylphthalocyanine. The copper octa[di ([3 acetoxyethyl)aminomethyl] octaphenylphthalocyanine so obtained is soluble in acetone and gives fast green shades when used in the mass colouration of cellulose acetate rayon.

Copper octa [di 8 hydroxyethyl)aminomethyl]- octaphenylphthalocyanine may be obtained as described in Example 22 of British application No. 11,399/58.

Example 7 with acetone and evaporation of the acetone solution.

The copper tri(fl-acetoxyethylsulphamyl)phthalocyanine so obtained is readily soluble in acetone and may be used in the mass colouration' of cellulose acetate rayon giving bright greenish blue shades'of outstanding fastness to light and wet treatments.

The copper tri(fi-hydroxyethylsulphamyl)phthalocyanine used in this example may be obtained as follows:

12.5 parts of copper phthalocyanine is added to 40 parts of chlorosulphonic acid and stirred until dissolved,

' then heated to 120 C for 2 hours. After this time the solution is cooled to 80 C. and 5 parts of thionyl chloride is added during 15 minutes. The mixture'is then heated used 5 parts of copper tetra-[diw-hydroxyethyl)amino methyl1-tetraphenylphthalocyanine. The copper tetrarequired to keepthe temperature below 0 C. The precipitated copper phthalocyanine trisulphonyl chloride is filtered ofi and the filter cake issuspended in parts of water at 0 C. 10% aqueous sodium bicarbonate solution is added until the mixture is no longer acid to Congo Red paper, the temperature being kept at 0 C. by addition of ice to the mixture when necessary- 35 parts of fi-hydroxyethylamine is then added and thernixture is stirred for 16 hours at atmospheric temperature and then for 1 hour at 60 C. The insoluble copper tri(,B-hydroxyethylsulphamyl)phthalocyanine is filtered off, washed and dried. A

Example .8

In place o t the 10 parts of copper tri-(dhydroxyethyl sulphamyDphthalocyanine used in Example 7 there is used 10 parts of copper tetra-(13-hydroxyethylsulphamyl) phthalocyaninec The copper tetra-(fi-acetoxyethylsulpha myDphthalocyanine so obtained is soluble in acetone and may be used in the mass colo'uration of cellulose acetate, Y

giving bright greenish blue shades of outstanding fastness to light to wetjtreatments; V 7

Copper tetra (tihydroxyethylsulphamyl)phthalocya nine may be obtained by a procedure exactly similar to that described in Example Tim the "corresponding tri- (p-hydroxyethylsulphamyl) compound,'except that the solution of copperphthalocyanine in chlofosulphonic acid is heated to 140 C. for 2 hours instead of 120 C. for 2 /2 hours.

Example 9 In place of the parts of copper tri-(B-hydroxyethfsulpharnyDphthalocyanine used in Example 7 there is used 10 parts of copper tetra-[di-(p-hydroxyethyl)sulphamyllphthalocyanine. The copper tetra [di- (p-acetoxyethyl)sulphamylJphthalocyanine so obtained is soluble in acetone and may be used in the mass colouration of cellulose acetate, giving bright greenish blue shades of outstanding fastness to light and to Wet treatments.

Copper tetradi- (fi-hydroxyethyl) sulphamyl] phthalocyanine may be obtained by a procedure similar to that described in Example 8 for the corresponding tetra-(shy droxyethylsulphamyl) compound, except that di-(fi-hydroxyethyl) amine is used in place of B-hydroxyet'nylamine.

Example 11 Using procedures closely similar to those given in Examples 7, 8, 9 and 10 copper phthalocyanine trior tetrasnlphonyl chloride may be reacted with N-methyl ethanolamine, N-ethyl ethanolamine, 2 methyl 2 hydroxy-npentylamine; N-(Z-hydroxyethyl) N (2-hydroxybutyl) amine or N :N-di(2-hydroxy-n-propyl)amine to give hydroxyalkylsulphamyl compounds which may then be acetylated by boiling with acetic anhydride. The products are all soluble in acetone and are suitable for use in the mass colouration of cellulose acetate rayon, giving bright greenish blue shades which have excellent fastness to light and to wet treatments.

Example 12 12 parts of a mixture of nickel triand tetra-(,B-hy-' droxyethylsulphamyl)phthalocyanine is stirred with 60 parts of acetic anhydride and boiled under reflux for 4 hours. The mixture is cooled and diluted With 500 parts of cold Water, and made just alkaline to Brilliant Yellow paper by the addition of aqueous sodium hydroxide solution. The product is filtered off and dried.

The dry solid is dissolved in acetone and the solution filtered from insoluble material. By evaporation of the acetone solution a mixture of nickel triand tetra-(fl-acetoxyethylsulphamyl)phthalocyanine is obtained. The product is suitable for use in the mass colouration of cellulose acetate rayon and gives blue shades of high fastness to light and wet treatments.

The mixture of nickel triand tetra-(fi-hydroxyethylsulphamyl)phthalocyanine used in this example may be obtained by using nickel phthalocyanine in place of copper phthalocyanine in the procedure described in Example 7 for obtaining copper tri(fl-hydroxyethylsulphamyl)- phthalocyanine.

Example 13 In place of the 12 parts of nickel triand tetra-(B-hydroxyethylsulphamyl)phthalocyanine used in Example 12, there is used 12 parts of nickel triand tetra-[diQS-hydroxyethyl) sulphamylJphthalocyanine. The nickel triand tetra- [di (fl-acetoxyethyl sulphamyl1phthalocyanine filtered from insoluble material.

so obtained is soluble in acetone and may be used in the mass colouration of cellulose acetate rayon, giving blue shades of good fastness. I

The nickel triand tetra-[di(fi-hydroxyethyl) sulphamyl] phthalocyanine may be obtained by a procedure exactly similar to that described in Example 7 for copper tri-[,B-hydroxyethylsulphamyl]phthalocyanine except that nickel phthalocyanine is used in place of copper phthalocyanine and di-(fi-hydroxyethyl) amine is used in place of fl-hydroxyethylamine.

Example 14 10 parts of cobalt tri(/i-hydroxyethylsulphamyl)- phthalocyanine is stirred with 50 parts of acetic anhydride and boiled under reflux for four hours. The mixture is cooled and diluted with 500 parts of cold water and neutralized by the addition of aqueous caustic soda solution. The product is filtered off and dried. The dry solid is dissolved in acetone and the solution is filtered from insoluble material. By evaporation of the acetone solu tion cobalt tri-(5-acetoxyethylsulphamyl)phthalocyanine is obtained. The product is suitable for use in the mass colouration of cellulose acetate rayon, and gives blue shades of high fastness.

Cobalt tri-(fi-hydroxyethylsulphamyl)phthalocyanine may be obtained by a procedure exactly similar to that used in Example 7 for copper triQB-hydroxyethylsulphamyDphthaIocyanine, except that cobalt phthalocyanine is used in place of copper phthalocyanine.

Example 15 In place of the 10 parts of cobalt tri(/8-hydroxyethy1- sulphamyDpthalocyanine used in Example 14, there is used 10 parts of cobalt tri-[di-(,8-hydroxyethyl)sulphamyl]phthalocyanine. The cobalt tri-[di-(fl-acetoxyethyl)sulphamylJphthalocyanine so obtained is soluble in acetone and may be used in the mass colouration of cellulose acetate rayon, giving blue shades of good fastness.

Cobalt tri- [di s-hydroxyethyl) sulphamyl] phthalocyanine may be obtained by a procedure exactly similar to that described in Example 7 for copper tri(;8-hydroxyethylsulphamyl)phthalocyanine except cobalt phthalocyanine is used in place of copper phthalocyanine and di- (fi-hydroxyethyDamine is used in place of ,B-hydroxyethylamine.

Example 16 10 parts of copper tetra-4-chloro triQS-hydroxyethylsulphamyDphthalocyanine is stirred with 50 parts of acetic anhydride and boiled under reflux for 4 hours. The mixture is cooled and diluted with 500 parts of cold Water, and neutralised by the addition of aqueous sodium hydroxide solution. The product is filtered off and dried. The dry solid is dissolved in acetone, and the solution is By evaporation of the acetone solution copper tetra-4-chloro tri(fl-acetoxyethyl)- sulphamyl phthalocyanine is obtained. The product is suitable for use in the mass colouration of cellulose acetate rayon and gives greenish-blue shades of high fastness.

Copper tetra-4-chloro tri-(B-hydroxyethylsulphamyl)- phthalocyanine may be obtained by reacting copper tetra- 4-chlorophthalocyanine tri-sulphonchloride with fi-hydroxy-ethylamine. Copper tetrachlorophthalocyanine trisulphonchloride may be obtained by heating a mixture of 36 parts copper tetra-4-chlorophthalocyanine with 100 parts chlorosulphonic acid at 120 C. for 3 hours, cooling to C. and adding 15 parts of thionylchloride, then heating at C. for 2 hours. The solution is cooled and poured into ice and water, adding ice as required to keep the temperature below 0 C., and the precipitated copper tetrachlorophthalocyanine trisulphonchloride is filtered ofi.

Example 17 In place of the 10 parts of copper tetra-4-chloro tri(,B- hydroxyethylsulphamyl)phthalocyanine used in Example tetral-chloro "filtered from insoluble material.

7 .16, there is used 10 parts of copper tetra-4-chloro-tri-(di- (fl-hydroxyethyl)sulphamyl)phthalocyanine. The copper tri(di(,6-acetoxyethyl)sulphamyl)phthalocyanine so obtainedis soluble in acetone and may be used in the mass colour'ationof cellulose acetate rayon, giving greenish blue shades of good fastness.

Copper tetra-4-chloro tri-(di(/8-hydroxyethyl)sulphamyl)phthalocyanine may be obtained by a procedure exactly similar to that described in Example 16 for copper tetrachloro tri B-hydroxyethylsulphamyl phthalo cyanine except that di(,8-hydroxyethyl)amine is used in place of fi-hydroxyethylamine.

7 Example 18 10 parts of copper tri-(,B-hydroxyethylsulphamyl)- phthalocyanine and parts of acetylchloride is stirred for 4 hours at 100 C. The mixture is cooled, diluted with 400 parts of Water and stirred to decompose excess acetyl chloride. The product is filtered off, Washed, and dried. The copper tri(fi-acetoxyethylsulphamyl)phthalocyanine obtained may be separated from some insoluble matter by dissolving in acetone, filtering oil and evaporating to dryness. The properties of the product are identical with those of the product of Example 7.

' Example 19 Example 20 10 parts of a mixture of copper diand tri-[di(-hydroxyethyl)-aminornethyl]phthalocyanine is stirred with '50 parts of acetylchloride and boiled under reflux for 4 hours. The mixture is cooled and diluted with 500 parts of cold water, and neutralised' by the addition of aqueous sodium carbonate solution. The product is filtered oil and dried.

The dry solid is dissolved in acetone and the solution acetone a mixture of copper diand tri-[di(B-acetoxyethyl) aminomethyflphthalocyanine is obtained. The properties of the product are identical wtih those of the product of Example 1. f

Example 21 erties with the product of Example 7.

Example 22 chloride used in Example 21, there is used 32 parts of d i(flacetoxyethyl) amine hydrochloride. Copper tri-(di- By evaporation of the 7 In place of the 20 parts of B-acetoxyethylamine hydro- Example 23 In place of the 10 parts of copper tri(B-hydroxyethy1- sulphamyDphthalocyanine used in Example 7 there is used 10 parts of. copper monosulpho-tri-[di-(fi-hydroxyethyl)sulphamyl1phthalocyanine. The copper monosulpho tri- [di- B-acetoxyethyl) sulphamyl1phthalocyanine salt obtained is soluble in acetone and is suitable for use in the mass colouration of cellulose acetate;

Copper monosulpho tri [di (,8 hydroxyethyl)sulphamyflphthalocyanine may be obtained by a procedure similar to the described in Example 7 for copper tri- (B-hydroxyethylsulphamyl)phthalocyanine except that the solution of copper phthalocyanine in chlorosulphonic acid is heated to 140 C. for 2 hours instead of C. for 2 /2 hours, and that 17 parts of di(fi-hydroxyethyl)amine is used in place of 35 parts of B-hydroxyethylamine.

What We claim is:

l. A compound of the formula wherein Pc represents a metal phth-alocyanine radical and selected from the class consisting of the unsubstituted metal phthalocyanine, chlorosubstituted phthalocy-anine, monocylic aryl substituted phthalocyanine, monocylic arylthio-suhstituted phthalocyanine, monocyclic arylcarbonyl-s'ubstituted phthalocyanine and monocyclic aryl sulphamyl-substituted phthalocyanine;

the metal is selected ,from the group consisting of copper cobalt, nickel, iron, aluminum and chromium;

X represents a divalent radical, selected from the class consisting of CH and --S) R represents lower alkylene;

R represents a monovalent radical, selectedfrorn the class consisting of lower alkyl, phenyl and chlorophenyl;

R represents a monovalent radical, selected from the class consisting of hydrogen, lower alkyl and the grouping -R4O-( lR2 wherein R is lower alkylene; and n is an integer from 2 to 8. i

2. Copper tetra-(fi-acetoxyethylsulphamyl)phthalocy- 5. Copper tri-[di-(fi-acetoxyethyl)sulphamyHphthalocyanine.

References Cited in the file of this patent UNITED STATES PATENTS Randall et a1. Apr. 10, 1951 OTHER REFERENCES Wagner et al;: Synthetic Organic Chemistry, Wiley, New York, N.Y. (1953), pages 481 and 482. 

3. COPPER TETRA-$DI-(B-ACETOXYETHYL)SULPHAMYL$PHTHALOCYANINE. 